2807
Anal, Chem. 1084, 56,2607-2610
ethanyl]-1,3,3-trimethyl-3H-indolium cation, 92078-57-4.
300
100 0 -
LITERATURE CITED
315
50 0 -
Flgure 8. CAD spectrum of m l z 315 from Basic Orange 21.
ions at m/z 180 and 198 gave very similar CAD spectra, both strongly suggestive of hydrocarbons, and are presumed to arise from solvents used in manufacture of the dye (15). Results obtained with dyes of other classes, including anthraquinones, xanthenes, coumarins, arylmethanes, sulfonephthaleins, and azo compounds will be presented elsewhere.
ACKNOWLEDGMENT The hydrogenation of Basic Red 14 was performed by R. L. Titus, Department of Chemistry, University of NevadaLas Vegas. Registry No. 3,47474-85-1;4, 42279-64-1; 1,3,3-trimethyl-2methyleneindoline, 118-12-7; 4-[(2-~yanoethyl)methylamino]benzaldehyde, 94-21-3; basic red 14,12217-48-0;basic orange 21, 3056-93-7; 2- [ 2- [ 4- [ (2-cyanoethyl)methylamino]phenyl]-
McEwen, C. N.; Layton, S. F.; Taylor, S. K. Anal. Chem. 1977, 4 9 , 922. Grahn, W. Liebigs Ann. Chem. 1981, ( I ) , 107. Monaghan, J. J.: Barber, M.; Bordoll, R. S.; Sedgwick, R. D.: Tyler, A. N. Int. J. Mass Spectrom. Ion Phys. 1983, 46, 447. Schelfers, S. M.; Verma, S.; Cooks, R. G. Anal. Chem. 1983, 55, 2260. Barofsky, D. F.; Glessmann, U. Int. J . Mass Spectrom. Ion Phys. 1983, 4 6 , 359. Mathias, A.; Wllllams, A. E.; Games, D. E.; Jackson, A. H. Org. Mass Spectrom. 1976, 1 1 , 266. Schulten, H. R.; Kuemmler, D. Fresenius' Z . Anal. Chem. 1976, 278, 13. Blakelv, C. R.: Carmodv. J. J.: Vestal. M. L. J . Am. Chem. SOC. 1980,-102, 5931. Blakely, C. R.; Vestal, M. L. Anal. Chem. 1983, 55, 750. Llberato, D. J.; Fenselau, C. C.; Vestal, M. L.; Yergey, A. L. Anal. Chem. 1983, 55, 1741. Covey, T; Henlon, J. Anal. Chem. 1983, 55, 2275. Betowski, L. D.; Ballard, J. M., unpublished work, Las Vegas, NV, 1984. Games, L. M.; Hltes, R. A. Anal. Chem. 1977, 4 9 , 1433. Allen, R. L. M. "Colour Chemistry"; Appleton-Century-Crofts: New York, 1971; Chapter 8. German Patent DE 3 136 583; Chem. Abstr. 1983, 9 9 , 24030e.
Leon D. Betowski* Environmental Protection Agency Environmental Monitoring Systems Laboratory Las Vegas, Nevada 89114 John M. Ballard Lockheed Engineering and Management Services Company, Inc. P.O. Box 15027 Las Vegas, Nevada 89114
RECEIVED for review May 17, 1984. Accepted July 16,1984.
Integrated Method for Determining NO, Emissions at Nitric Acid Plants Sir: The phenoldisulfonic acid method, Method 7 ( I ) , has been promulgated by EPA as the reference method for measurement of NO, (NO NOz) emissions in nitric acid plant stacks. In this method, a sample is collected with an evacuated 2-L flask over approximately a 15-s period. Sampling for only 15 s, of course, does not provide a representative sampling of emissions, because the NO, concentration in a stack changes with time as the process changes. In practice, numerous Method 7 samples are necessary to obtain a representative NO, value. This paper describes work on the evaluation of two manual integrated-sampling methods that use an alkaline-permanganate collection solution to determine NO, emissions. An important part of the work involved quantification of the interference from NH3. These integrated methods could also be used in place of Method 7 to determine the relative accuracy of continuous emission NO, monitors, as required by EPA (2);this change would reduce the number of samples required by a factor of 3.
+
EXPERIMENTAL SECTION Nitric Acid Plant. The nitric acid plant sampled was Nitram, Inc., located in Tampa, FL. The facility contains two plants, both of which produce HN03by oxidation of NH, over a Pt-Rh catalyet (3). The emission control process uses NH3 injection in which the NO, emissions and an excess of NH, are adsorbed on a mo-
lecular sieve. The molecular sieve catalyzes the NO,-", reaction to produce N2and H 2 0the NH3 concentration emitted from each stack is different. One stack at Nitram typically emitted 50 ppm NH3 and the other 200 pprn NHB. The actual sample matrix, exclusive of NH3 concentration,which is discussed in the text, for all four runs was NO, (-70% NO + -30% NO&, 2.6%-3.0% V / V 0 2 ,
